The present invention relates to magnetic acicular composite particles for magnetic recording medium, and a magnetic recording medium using the black magnetic acicular composite particles. More particularly, the present invention relates to magnetic acicular composite particles exhibiting not only an excellent dispersibility in vehicle due to a less amount of carbon black desorbed or fallen-off from the surfaces thereof, but also a more excellent blackness, a lower volume resistivity value and a well-controlled myristic acid-adsorption; and a magnetic recording medium exhibiting not only a smooth surface, a smaller light transmittance and a lower surface electrical resistivity value, but also a small friction coefficient and an excellent running durability.
With a development of miniaturized, lightweight video or audio magnetic recording and reproducing apparatuses for long-time recording, magnetic recording media such as a magnetic tape and magnetic disk have been increasingly and strongly desired to have a higher performance, namely, a higher recording density, higher output characteristic, in particular, an improved frequency characteristic and a lower noise level.
Especially, video tapes have recently been desired more and more to have a higher picture quality, and the frequencies of carrier signals recorded in recent video tapes are higher than those recorded in conventional video tapes. In other words, the signals in the short-wave region have come to be used, and as a result, the magnetization depth from the surface of a magnetic tape has come to be remarkably small.
In order to enhance output characteristics of magnetic recording media, especially an S/N ratio thereof with respect to signals having a short wavelength, there have been demanded fineness of magnetic particles, reduction in thickness of a magnetic recording layer, high dispersibility of magnetic particles and surface smoothness of a magnetic coating film.
On the other hand, at the present time, the end position of a magnetic recording medium such as magnetic tapes has been detected by sensing a high light transmittance portion of the magnetic recording medium by means of a video deck. In the case where the particle size of magnetic particles dispersed in the magnetic recording layer become finer and the thickness of the magnetic recording medium is reduced in order to meet the requirement for high performance of the magnetic recording medium as described hereinbefore, the magnetic recording medium shows a high light transmittance as a whole, so that it has been difficult to detect the end position thereof by means of the video deck. In order to solve this problem, carbon black fine particles have been added to the magnetic recording layer in an amount of usually about 6 to 12 parts by weight based on 100 parts by weight of the magnetic particles, thereby reducing the light transmittance of the magnetic recording medium. For this reason, in current videotapes, it is essential to add carbon black fine particles, etc., to the magnetic recording layer thereof.
However, when a large amount of such non-magnetic carbon black fine particles are added to the magnetic recording layer, the magnetic recording medium suffers from deterioration in signal recording property, thereby hindering high-density recording thereon, and the reduction in thickness of the magnetic recording layer becomes incapable. Further, due to the fact that the carbon black fine particles have an average particle size as fine as 0.002 to 0.05 xcexcm and a large BET specific surface area value, and are deteriorated in solvent-wettability, it has been difficult to disperse these carbon black fine particles in vehicle, thereby failing to obtain a magnetic recording medium having a smooth surface.
Further, in the case where the magnetic recording medium has a high surface electrical resistivity, the electrostatic charge amount thereof is increased, so that cut chips or dusts tend to adhere onto the surface of the magnetic recording medium upon the production or use thereof, thereby causing such a problem that the dropout frequently occurs. Therefore, in order to reduce not only the light transmittance of the magnetic recording medium but also the surface electrical resistivity thereof, especially below about 108 xcexa9/cm2, the carbon black fine particles have been conventionally added to the magnetic recording layer of the magnetic recording medium.
However, as described above, in the case where the amount of such carbon black fine particles or the like which do not contribute to magnetic properties of the magnetic recording layer, is increased, there are caused such problems that the magnetic recording medium suffers from deterioration in signal recording property, the reduction in thickness of the magnetic recording layer becomes incapable, and further the surface smoothness of the magnetic recording layer is deteriorated.
Also, since the carbon black fine particles are bulky particles having a bulk density as low as about 0.1 g/cm3, the handling property and workability thereof are deteriorated. In addition, it has been pointed out that the use of such carbon black fine particles causes problems concerning safety and hygiene such as carcinogenesis.
Magnetic recording media have been continuously required to enhance performances thereof. In particular, it has been strongly required to improve physical properties of these magnetic recording media such as running property in addition to the above-described high-density recording property.
The running property of magnetic recording media (tapes) can be ensured by adding a fatty acid such as myristic acid or stearic acid (hereinafter referred to merely as xe2x80x9cmyristic acidxe2x80x9d) in an amount of usually about 0.5 to 5% by weight based on the weight of magnetic particles, into a magnetic recording layer generally formed as an upper layer of the respective magnetic recording medium, and then allowing the myristic acid to be gradually oozed out on the surface of the magnetic recording layer so as to render the surface slidable.
When the amount of the myristic acid oozed out on the surface of the magnetic recording layer is too small, it is not possible to ensure a good running property of the magnetic recording media. On the contrary, when a large amount of the myristic acid is added to the magnetic recording layer so as to allow a large amount of myristic acid to be subsequently oozed out on the surface thereof, the myristic acid is preferentially adsorbed onto the surface of each magnetic particle dispersed in the magnetic recording layer, thereby inhibiting the magnetic particles from being contacted with or adsorbed into resins. As a result, it is difficult to disperse the magnetic particles in vehicle. Also, the increase in amount of the myristic acid as a non-magnetic component causes deterioration in magnetic properties of the magnetic recording media. Further, since the myristic acid acts as a plasticizer, there arise problems such as deterioration in mechanical strength of the magnetic recording media.
Recently, with further reduction in thickness of the magnetic recording layer, the absolute amount of myristic acid added to the magnetic recording layer is decreased. In addition, since the particle size of the magnetic particles have become much finer in order to meet the requirement of high-density recording, the BET specific surface area thereof is increased, so that a large amount of myristic acid is absorbed onto the surfaces of the magnetic particles. Under these conditions, it is more and more difficult to properly adjust the amount of the myristic acid oozed out on the surface of the magnetic recording layer by the amount of the myristic acid added into the magnetic recording layer, thereby ensuring a good running property of the magnetic recording layer.
Accordingly, it has been strongly required to properly adjust the amount of myristic acid oozed out on the surface of the magnetic recording layer and ensure a good running property of the magnetic recording media.
In order to improve electrical resistance and running durability of the magnetic recording media, there have been proposed such magnetic particles on the surfaces of which carbon and/or graphite are deposited or adhered in an amount of 0.2 to 10.0% by weight based on the weight of the magnetic particles (corresponding to 0.2 to 11.11 parts by weight based on 100 parts by weight of the magnetic particles) by various methods such as gas-phase growth, e.g., chemical vapor deposition (CVD) or physical vapor deposition (PVD), reduction of organic compounds, and thermal decomposition or incomplete combustion of hydrocarbons (Japanese Patent Application Laid-Open (KOKAI) No. 10-269558(1998)).
Also, hitherto, with the reduction in thicknesses of magnetic recording layer and non-magnetic base film of magnetic recording media, it has been variously attempted to impart good surface smoothness and large stiffness thereto by improving a substrate on which the magnetic recording layer is formed. For instance, there has been proposed a non-magnetic substrate composed of a non-magnetic base film and at least one undercoat layer formed on the non-magnetic base film. The undercoat layer is composed of a binder and non-magnetic particles dispersed in the vehicle, which contain iron as a main component, e.g., acicular hematite particles or acicular iron oxide hydroxide particles (hereinafter referred to merely as xe2x80x9cnon-magnetic undercoat layerxe2x80x9d). Such a non-magnetic substrate is already put into practice (refer to Japanese Patent Publication (KOKOKU) No. 6-93297(1994), Japanese Patent Application Laid-Open (KOKAI) Nos. 62-159338(1987), 63-187418(1988), 4-167225(1992), 4-325915(1992), 5-73882(1993), 5-182177(1993), 5-347017(1993) and 6-60362(1994), or the like).
As non-magnetic particles for the non-magnetic undercoat layer, there have been known non-magnetic particles which are treated with a hydroxide of aluminum, an oxide of aluminum, a hydroxide of silicon or an oxide of silicon in order to improve a dispersibility of these particles in vehicle, etc., for further smoothening the surface of a substrate and increasing the stiffness thereof (Japanese Patent Nos. 2,571,350 and 2,582,051, and Japanese Patent Application Laid-Open (KOKAI) Nos. 6-60362(1994), 9-22524(1997) and 9-27117(1997)).
Also, in order to reduce a light transmittance of magnetic recording media by reducing the amount of carbon black added to a magnetic recording layer thereof, it has been known to use as non-magnetic particles for non-magnetic undercoat layer, blackish brown acicular hematite particles or blackish brown acicular iron oxide hydroxide particles (Japanese Patent Application Laid-Open (KOKAI) Nos. 7-66020(1995), 8-259237(1996) and 9-167333(1997) or the like). Further, it has been known to use non-magnetic acicular particles which are composed of acicular hematite particles or acicular iron oxide hydroxide particles as core particles and carbon black fine particles adhered onto the surfaces of the core particles in an amount of 1 to 20 parts by weight based on 100 parts by weight of the core particles (European Patent No. 0,824,690 A).
Also, it has been known that mixed particles composed of non-magnetic iron oxide particles and carbon black particles are used as non-magnetic particles for non-magnetic undercoat layer in order to reduce the surface electrical resistivity value of magnetic recording media (Japanese Patent Application Laid-Open (KOKAI) Nos. 1-213822(1989), 1-300419(1989), 6-236542(1994) and 9-297911(1997) or the like).
At present, it has been strongly demanded to provide magnetic recording media which exhibit not only a smooth surface, a smaller light transmittance and a lower surface electrical resistivity value, but also a small friction coefficient and an excellent running durability. However, magnetic recording media satisfying all of these properties have not been obtained until now.
As a result of the present inventors"" earnest studies in view of the above problems, it has been found that by using as magnetic particles for magnetic recording medium, black magnetic acicular composite particles comprising:
as core particles magnetic acicular cobalt-coated iron oxide particles or magnetic acicular metal particles containing iron as a main component;
a coating formed on surface of the core particle, comprising at least one organosilicon compound selected from the group consisting of:
(1) organosilane compounds obtainable from alkoxysilane compounds, and
(2) polysiloxane or modified polysiloxane; and
a single carbon black coat (carbon black-coating monolayer) formed on the coating layer comprising the organosilicon compound, in an amount of from more than 10 to 40 parts by weight based on 100 parts by weight of said core particles,
the obtained magnetic recording medium can exhibit not only a smooth surface, a smaller light transmittance and a lower surface electrical resistivity value, but also a small friction coefficient and an excellent running durability. The present invention has been attained based on this finding.
An object of the present invention is to provide a magnetic recording medium exhibiting not only a smooth surface, a smaller light transmittance and a lower surface electrical resistivity value, but also a small friction coefficient and an excellent running durability.
Another object of the present invention is to provide magnetic acicular particles exhibiting not only an excellent dispersibility in vehicle due to a less amount of carbon black desorbed or fallen-off from the surfaces thereof, but also a more excellent blackness, a lower volume resistivity value and a well-controlled myristic acid-adsorption.
To accomplish the aims, in a first aspect of the present invention, there is provided a magnetic recording medium comprising:
a non-magnetic base film; and
a magnetic recording layer formed on the non-magnetic base film, comprising a binder resin and black magnetic acicular composite particles having an average particle diameter of 0.051 to 0.35 xcexcm, which black magnetic acicular composite particles comprise:
as magnetic acicular particles, magnetic acicular cobalt-coated iron oxide particles or magnetic acicular metal particles containing iron as a main component
a coating formed on surface of the magnetic acicular particles, comprising at least one organosilicon compound selected from the group consisting of:
(1) organosilane compounds obtainable from alkoxysilane compounds, and
(2) polysiloxanes or modified polysiloxanes and
a single carbon black coat formed on the coating layer comprising the organosilicon compound, in an amount from more than 10 to 40 parts by weight based on 100 parts by weight of said magnetic acicular particles.
In a second aspect of the present invention, there is provided a magnetic recording medium comprising:
a non-magnetic base film; and
a magnetic recording layer formed on the non-magnetic base film, comprising a binder resin and black magnetic acicular composite particles having an average particle diameter of 0.051 to 0.35 xcexcm. which black magnetic acicular composite particles comprise:
as magnetic acicular particles, magnetic acicular cobalt-coated iron oxide particles or magnetic acicular metal particles containing iron as a main component, which have a coat formed on at least a part of the surface of the magnetic acicular particle, comprising at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon in amount of 0.01 to 20% by weight, calculated as Al or SiO2, based on the weight of the magnetic acicular particles coated,
a coating layer formed on surface of the coat on the magnetic acicular particles, comprising at least one organosilicon compound selected from the group consisting of:
(1) organosilane compounds obtained obtainable from alkoxysilane compounds, and
(2) polysiloxanes or modified polysiloxanes, and
a single carbon black coat formed on the said coating layer comprising the said organosilicon compound, in an amount of from more than 10 to 40 parts by weight based on 100 parts by weight of the said magnetic acicular particles.
In a third aspect of the present invention, there is provided a magnetic recording medium comprising:
a non-magnetic base film;
a non-magnetic undercoat layer formed on the non-magnetic base film; and
a magnetic recording layer formed on the non-magnetic undercoat layer, comprising a binder resin and black magnetic acicular composite particles having an average particle diameter of 0.051 to 0.35 xcexcm, which black magnetic acicular composite particles comprise:
as magnetic acicular particles, magnetic acicular cobalt-coated iron oxide particles or magnetic acicular metal particles containing iron as a main component,
a coating formed on surface of said magnetic acicular particles, comprising at least one organosilicon compound selected from the group consisting of:
(1) organosilane compounds obtainable from alkoxysilane compounds, and
(2) polysiloxanes or modified polysiloxanes, and
a single carbon black coat formed on the coating layer comprising said organosilicon compound, in an amount of from more than 10 to 40 parts by weight based on 100 parts by weight of the magnetic acicular particles.
In a fourth aspect of the present invention, there is provided a magnetic recording medium comprising:
a non-magnetic base film;
a non-magnetic undercoat layer formed on the non-magnetic base film; and
a magnetic recording layer formed on the non-magnetic undercoat layer, comprising a binder resin and black magnetic acicular composite particles having an average particle diameter of 0.051 to 0.35 xcexcm, which black magnetic acicular composite particles comprise:
as magnetic acicular particles, magnetic acicular cobalt-coated iron oxide particles or magnetic acicular metal particles containing iron as a main component, which have a coat formed on at least a part of the surface of the magnetic acicular particle, comprising at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon in amount of 0.01 to 20% by weight, calculated as Al or SiO2, based on the weight of the magnetic acicular particles coated,
a coating layer formed on surface of the coat on the magnetic acicular particles, comprising at least one organosilicon compound selected from the group consisting of:
(1) organosilane compounds obtained obtainable from alkoxysilane compounds, and
(2) polysiloxanes or modified polysiloxanes, and
a single carbon black coat formed on the said coating layer comprising the said organosilicon compound, in an amount of from more than 10 to 40 parts by weight based on 100 parts by weight of the said magnetic acicular particles.
In a fifth aspect of the present invention, there are provided black magnetic acicular composite particles for a magnetic recording medium, having an average particle diameter of 0.051 to 0.35 xcexcm, comprising:
as magnetic acicular particles, magnetic acicular cobalt-coated iron oxide particles or magnetic acicular metal particles containing iron as a main component,
a coating formed on surface of said magnetic acicular particles, comprising at least one organosilicon compound selected from the group consisting of:
(1) organosilane compounds obtainable from alkoxysilane compounds, and
(2) polysiloxanes or modified polysiloxanes, and
a single carbon black coat formed on said coating layer comprising said organosilicon compound, in an amount of from more than 10 to 40 parts by weight based on 100 parts by weight of said magnetic acicular particles.
In a sixth aspect of the present invention, there are provided black magnetic acicular composite particles for a magnetic recording medium, having an average particle diameter of 0.051 to 0.35 xcexcm, comprising:
as magnetic acicular particles, magnetic acicular cobalt-coated iron oxide particles or magnetic acicular metal particles containing iron as a main component, which have a coat formed on at least a part of the surface of the magnetic acicular particle, comprising at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon in amount of 0.01 to 20% by weight, calculated as Al or SiO2, based on the weight of the magnetic acicular particles coated,
a coating layer formed on surface of the coat on the magnetic acicular particles, comprising at least one organosilicon compound selected from the group consisting of:
(1) organosilane compounds obtainable from alkoxysilane compounds, and
(2) polysiloxanes or modified polysiloxanes, and
a single carbon black coat formed on the coating layer comprising said organosilicon compound, in an amount of from more than 10 to 40 parts by weight based on 100 parts by weight of the said magnetic acicular particles.
The present invention will be described in detail below.
First, the magnetic recording medium according to the present invention is described.
The magnetic recording medium according to the present invention has the following constructions.
(1) A magnetic recording medium comprises a non-magnetic base film; and a magnetic recording layer formed on the non-magnetic base film, which comprises as magnetic particles, black magnetic acicular composite particles and a binder resin.
(2) A magnetic recording medium comprises a non-magnetic base film; a non-magnetic undercoat layer formed on the non-magnetic base film, which comprises non-magnetic particles and a binder resin; and a magnetic recording layer formed on the non-magnetic undercoat layer, which comprises as magnetic particles, black magnetic acicular composite particles and a binder resin.
The black magnetic acicular composite particles having an average particle diameter of 0.051 to 0.35 xcexcm according to the present invention, comprise magnetic acicular particle as a core particle, a coating layer comprising an organosilicon compound which is formed on the surface of each magnetic acicular particle, and a single carbon black coat layer which are formed on the coating layer comprising the organosilicon compound.
As the magnetic acicular particles used as core particles in the present invention, there may be exemplified (a) magnetic acicular cobalt-coated iron oxide particles obtained by coating with cobalt, both cobalt and iron or the like the surface of as acicular magnetite particles (Fe3O4), acicular maghemite particles (xcex3-Fe2O3), acicular berthollide compounds particles (FeOx.Fe2O3; 0 less than X less than 1) which are intermediate oxides between maghemite and magnetite (hereinafter referred to merely as xe2x80x9cmagnetic acicular cobalt-coated iron oxide particlesxe2x80x9d); magnetic acicular metal particles containing iron as a main component which contain elements other than Fe such as Co, Al, Ni, P, Zn, Si, B or rare earth elements (hereinafter referred to merely as xe2x80x9cmagnetic acicular metal particlesxe2x80x9d) (which may include magnetic acicular iron alloy particles containing elements other than Fe such as Co, Al, Ni, P, Zn, Si, B or rare earth elements); or the like.
More specifically, the magnetic acicular metal particles may be exemplified as follows.
1) Magnetic acicular metal particles comprises iron; and cobalt of usually 0.05 to 40% by weight, preferably 1.0 to 35% by weight, more preferably 3 to 30% by weight (calculated as Co) based on the weight of the magnetic acicular metal particles.
2) Magnetic acicular metal particles comprises iron; and aluminum of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as Al) based on the weight of the magnetic acicular metal particles.
3) Magnetic acicular metal particles comprises iron; cobalt of usually 0.05 to 40% by weight, preferably 1.0 to 35% by weight, more preferably 3 to 30% by weight (calculated as Co) based on the weight of the magnetic acicular metal particles; and aluminum of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as Al) based on the weight of the magnetic acicular metal particles.
4) Magnetic acicular metal particles comprises iron; cobalt of usually 0.05 to 40% by weight, preferably 1.0 to 35% by weight, more preferably 3 to 30% by weight (calculated as Co) based on the weight of the magnetic acicular metal particles; and at least one selected from the group consisting of Nd, La and Y of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as the corresponding element) based on the weight of the magnetic acicular metal particles.
5) Magnetic acicular metal particles comprises iron; aluminum of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as Al) based on the weight of the magnetic acicular metal particles; and at least one selected from the group consisting of Nd, La and Y of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as the corresponding element) based on the weight of the magnetic acicular metal particles.
6) Magnetic acicular metal particles comprises iron; cobalt of usually 0.05 to 40% by weight, preferably 1.0 to 35% by weight, more preferably 3 to 30% by weight (calculated as Co) based on the weight of the magnetic acicular metal particles; aluminum of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as Al) based on the weight of the magnetic acicular metal particles; and at least one selected from the group consisting of Nd, La and Y of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as the corresponding element) based on the weight of the magnetic acicular metal particles.
7) Magnetic acicular metal particles comprises iron; cobalt of usually 0.05 to 40% by weight, preferably 1.0 to 35% by weight, more preferably 3 to 30% by weight (calculated as Co) based on the weight of the magnetic acicular metal particles; and at least one selected from the group consisting of Ni, P, Si, Zn, Ti, Cu and B of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as the corresponding element) based on the weight of the magnetic acicular metal particles.
8) Magnetic acicular metal particles comprises iron; aluminum of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as Al) based on the weight of the magnetic acicular metal particles; and at least one selected from the group consisting of Ni, P, Si, Zn, Ti, Cu and B of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as the corresponding element) based on the weight of the magnetic acicular metal particles.
9) Magnetic acicular metal particles comprises iron; cobalt of usually 0.05 to 40% by weight, preferably 1.0 to 35% by weight, more preferably 3 to 30% by weight (calculated as Co) based on the weight of the magnetic acicular metal particles; aluminum of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as Al) based on the weight of the magnetic acicular metal particles; and at least one selected from the group consisting of Ni, P, Si, Zn, Ti, Cu and B of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as the corresponding element) based on the weight of the magnetic acicular metal particles.
10) Magnetic acicular metal particles comprises iron; cobalt of usually 0.05 to 40% by weight, preferably 1.0 to 35% by weight, more preferably 3 to 30% by weight (calculated as Co) based on the weight of the magnetic acicular metal particles; at least one selected from the group consisting of Nd, La and Y of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as the corresponding element) based on the weight of the magnetic acicular metal particles; and at least one selected from the group consisting of Ni, P, Si, Zn, Ti, Cu and B of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as the corresponding element) based on the weight of the magnetic acicular metal particles.
11) Magnetic acicular metal particles comprises iron; aluminum of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as Al) based on the weight of the magnetic acicular metal particles; at least one selected from the group consisting of Nd, La and Y of ordinarily 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as the corresponding element) based on the weight of the magnetic acicular metal particles; and at least one selected from the group consisting of Ni, P, Si, Zn, Ti, Cu and B of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as the corresponding element) based on the weight of the magnetic acicular metal particles.
12) Magnetic acicular metal particles comprises iron; cobalt of usually 0.05 to 40% by weight, preferably 1.0 to 35% by weight, more preferably 3 to 30% by weight (calculated as Co) based on the weight of the magnetic acicular metal particles; aluminum of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as Al) based on the weight of the magnetic acicular metal particles; at least one selected from the group consisting of Nd, La and Y of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as the corresponding element) based on the weight of the magnetic acicular metal particles; and at least one selected from the group consisting of Ni, P, Si, Zn, Ti, Cu and B of usually 0.05 to 10% by weight, preferably 0.1 to 7% by weight (calculated as the corresponding element) based on the weight of the magnetic acicular metal particles.
The iron content in the magnetic acicular metal particles is the balance, and is preferably 50 to 99% by weight, more preferably 60 to 95% by weight (calculated as Fe) based on the weight of the magnetic acicular metal particles.
The core particles used in the present invention have an acicular shape. Meanwhile, the xe2x80x9cacicularxe2x80x9d used herein means xe2x80x9cspindle-shapedxe2x80x9d, xe2x80x9crice grain-likexe2x80x9d or the like in addition to literally xe2x80x9cacicular or needle-likexe2x80x9d.
As to the particle size of the magnetic acicular particles used in the present invention, the average major axial diameter thereof is preferably 0.05 to 0.34 xcexcm, more preferably 0.05 to 0.33 xcexcm, still more preferably 0.05 to 0.32 xcexcm.
When the average major axis diameter of the magnetic acicular particles is more than 0.34 xcexcm, the obtained black magnetic acicular composite particles also may become large particles. In the case where such large particles are used for forming a magnetic recording layer, the surface smoothness of the magnetic recording layer tends to be deteriorated. On the other hand, when the average particle size is less than 0.05 xcexcm, the intermolecular force between the particles may be increased due to the reduction in particle size, so that agglomeration of the particles tends to be caused. Therefore, it becomes difficult to uniformly coat the surfaces of the magnetic acicular particle with the organosilicon compound, and to uniformly form the carbon black coat on the surface of the coating layer comprising the organosilicon compounds.
The average minor axis diameter of the magnetic acicular particles as core particles used in the present invention is preferably 0.0025 to 0.17 xcexcm, more preferably 0.0025 to 0.165 xcexcm, still more preferably 0.0025 to 0.16 xcexcm.
The aspect ratio of the magnetic acicular particles as core particles used in the present invention (=average major axis diameter:average minor axis diameter, hereinafter referred to merely as xe2x80x9caspect ratioxe2x80x9d) is usually 2.0:1 to 20.0:1, preferably 2.5:1 to 18.0:1, more preferably 3.0:1 to 15.0:1. When the aspect ratio is more than 20.0:1, the magnetic acicular particles may tend to be entangled with each other, and it also may become difficult to uniformly coat the surfaces of the magnetic acicular particles with the organosilicon compounds and to uniformly form the carbon black coat on the surface of the coating layer comprising the organosilicon compounds. On the other hand, when the aspect ratio is less than 2.0:1, the strength of the coating film of the magnetic recording medium may be low.
The geometrical standard deviation value of the major axis diameter of the magnetic acicular particles as core particles used in the present invention is usually not more than 2.0, preferably not more than 1.8, more preferably not more than 1.6. When the geometrical standard deviation value thereof is more than 2.0, coarse particles may be contained therein, so that the magnetic acicular particles may be inhibited from being uniformly dispersed. Therefore, it may also become difficult to uniformly coat the surfaces of the magnetic acicular particles with the organosilicon compounds and to uniformly form the carbon black coat on the surface of the coating layer comprising the organosilicon compounds. The lower limit of the geometrical standard deviation value is 1.01. It is industrially difficult to obtain particles having a geometrical standard deviation value of less than 1.01.
The BET specific surface area of the magnetic acicular particles as core particles used in the present invention is usually 20 to 150 m2/g, preferably 25 to 120 m2/g, more preferably 28 to 100 m2/g. When the BET specific surface area is less than 20 m2/g, the magnetic acicular particles may become coarse, or the sintering between the particles may be caused, so that the obtained black magnetic acicular composite particles also may become coarse particles and tend to be deteriorated in smooth surface of the magnetic recording layer. When the BET specific surface area value is more than 150 m2/g, the particles may tend to be agglomerated together due to the increase in intermolecular force between the particles because of the fineness thereof, so that it may become difficult to uniformly coat the surfaces of the magnetic acicular particles with the organosilane compounds and to uniformly form the carbon black coat on the surface of the coating layer comprising the organosilicon compounds.
The blackness of the magnetic acicular particles as core particles used in the present invention, is usually more than 18.0 when represented by L* value, and the upper limit thereof is usually 34.0, preferably 32.0 when represented by L* value. When the L* value exceeds 34.0, the lightness of the particles may be high, so that it may be difficult to obtain black magnetic acicular composite particles having a sufficient blackness.
The volume resistivity value of the core particles is usually not less than 5xc3x971010 xcexa9xc2x7cm, preferably 1xc3x97106 to 1xc3x971010 xcexa9xc2x7cm.
The myristic acid-adsorption of the core particles is usually 0.4 to 1.5, preferably 0.4 to 1.2 mg/m2.
As to the magnetic properties of the magnetic acicular particles as core particles used in the present invention, the coercive force value thereof is usually 500 to 3500 Oe (39.8 to 278.5 kA/m), the saturation magnetization value is usually 60 to 170 emu/g (60 to 170 Am2/kg).
In case of magnetic acicular cobalt-coated iron oxide particles, the coercive force value thereof is usually 500 to 1700 Oe (39.8 to 135.3 kA/m), preferably 550 to 1700 Oe (43.8 to 135.3 kA/m); the saturation magnetization value is usually 60 to 90 emu/g (60 to 90 Am2/kg), preferably 65 to 90 emu/g (65 to 90 Am2/kg). In case of magnetic acicular metal particles containing iron as a main component, the coercive force value thereof is usually 800 to 3500 Oe (63.7 to 278.5 kA/m), preferably 900 to 3500 Oe (71.6 to 278.5 kA/m); the saturation magnetization value is usually 90 to 170 emu/g (90 to 170 Am2/kg), preferably 100 to 170 emu/g (100 to 170 Am2/kg).
The coating formed on the surface of the core particle comprises at least one organosilicon compound selected from the group consisting of (1) organosilane compounds obtainable from alkoxysilane compounds; and (2) polysiloxanes and modified polysiloxanes selected from the group consisting of (2-A) polysiloxanes modified with at least one compound selected from the group consisting of polyethers, polyesters and epoxy compounds (hereinafter referred to merely as xe2x80x9cmodified polysiloxanesxe2x80x9d), and (2-B) polysiloxanes whose molecular terminal is modified with at least one group selected from the group consisting of carboxylic acid groups, alcohol groups and a hydroxyl group (hereinafter referred to merely as xe2x80x9cterminal-modified polysiloxanesxe2x80x9d).
The organosilane compounds (1) may be produced by drying or heat-treating alkoxysilane compounds represented by the formula (I):                               R          a          1                ⁢        Si        ⁢                  xe2x80x83                ⁢                  X                      4            -            a                                              (        I        )            
wherein R1 is C6H5xe2x80x94, (CH3)2CHCH2xe2x80x94 or n-CbH2b+1xe2x80x94 (wherein b is an integer of 1 to 18); X is CH3Oxe2x80x94 or C2H5Oxe2x80x94; and a is an integer of 0 to 3.
The drying or heat-treatment of the alkoxysilane compounds may be conducted, for example, at a temperature of usually 40 to 200xc2x0 C., preferably 60 to 150xc2x0 C. for usually 10 minutes to 12 hours, preferably 30 minutes to 3 hours.
Specific examples of the alkoxysilane compounds may include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethyoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane or the like. Among these alkoxysilane compounds, in view of the desorption percentage and the adhering effect of carbon black, methyltriethoxysilane, phenyltriethyoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane and isobutyltrimethoxysilane are preferred, and methyltriethoxysilane and methyltrimethoxysilane are more preferred.
As the polysiloxanes (2), there may be used those compounds represented by the formula (II): 
wherein R2 is Hxe2x80x94 or CH3xe2x80x94, and d is an integer of 15 to 450.
Among these polysiloxanes, in view of the desorption percentage and the adhering effect of carbon black, polysiloxanes having methyl hydrogen siloxane units are preferred.
As the modified polysiloxanes (2-A), there may be used:
(a) polysiloxanes modified with polyethers represented by the formula (III): 
wherein R3 is xe2x80x94(xe2x80x94CH2xe2x80x94)hxe2x80x94; R4 is xe2x80x94(xe2x80x94CH2xe2x80x94)ixe2x80x94CH3; R5 is xe2x80x94OH, xe2x80x94COOH xe2x80x94CHxe2x95x90CH2, xe2x80x94C(CH3)xe2x95x90CH2 or xe2x80x94(xe2x80x94CH2xe2x80x94)jxe2x80x94CH3; R6 is xe2x80x94(xe2x80x94CH2xe2x80x94)kxe2x80x94CH3; g and h are an integer of 1 to 15; i, j and k are an integer of 0 to 15; e is an integer of 1 to 50; and f is an integer of 1 to 300;
(b) polysiloxanes modified with polyesters represented by the formula (IV): 
wherein R7, R8 and R9 are xe2x80x94(xe2x80x94CH2xe2x80x94)qxe2x80x94 and may be the same or different; R10 is xe2x80x94OH, xe2x80x94COOH, xe2x80x94CHxe2x95x90CH2, xe2x80x94C(CH3)xe2x95x90CH2 or xe2x80x94(xe2x80x94CH2xe2x80x94)rxe2x80x94CH3; R11 is xe2x80x94(xe2x80x94CH2xe2x80x94)sxe2x80x94CH3; n and q are an integer of 1 to 15; r and s are an integer of 0 to 15; exe2x80x2 is an integer of 1 to 50; and fxe2x80x2 is an integer of 1 to 300;
(c) polysiloxanes modified with epoxy compounds represented by the formula (V): 
wherein R12 is xe2x80x94(xe2x80x94CH2xe2x80x94)vxe2x80x94; v is an integer of 1 to 15; t is an integer of 1 to 50; and u is an integer of 1 to 300; or a mixture thereof.
Among these modified polysiloxanes (2-A), in view of the desorption percentage and the adhering effect of carbon black, the polysiloxanes modified with the polyethers represented by the formula (III), are preferred.
As the terminal-modified polysiloxanes (2-B), there may be used those represented by the formula (VI): 
wherein R13 and R14 are xe2x80x94OH, R16OH or R17COOH and may be the same or different; R15 is xe2x80x94CH3 or xe2x80x94C6H5; R16 and R17 are xe2x80x94(xe2x80x94CH2xe2x80x94)yxe2x80x94; y is an integer of 1 to 15; w is an integer of 1 to 200; and x is an integer of 0 to 100.
Among these terminal-modified polysiloxanes, in view of the desorption percentage and the adhering effect of carbon black, the polysiloxanes whose terminals are modified with carboxylic acid groups are preferred.
The coating amount of the organosilicon compounds is usually 0.02 to 5.0% by weight, preferably 0.03 to 4.0% by weight, more preferably 0.05 to 3.0% by weight (calculated as Si) based on the weight of the magnetic acicular particles coated with the organosilicon compounds.
When the coating amount of the organosilicon compounds is less than 0.02% by weight, it becomes difficult to coat the carbon black on the surfaces of the magnetic acicular particles.
On the other hand, when the coating amount of the organosilicon compounds is more than 5.0% by weight, a sufficient amount of the carbon black coat can be formed on the surfaces of the coating layer.
The carbon black coat constituted by a single carbon black coat is formed on at least a part of the surface of coating layer composed of the organosilicon compounds.
The amount of the single carbon black coat formed on the coating layer composed of the organosilicon compounds is usually from more than 10 part by weight to 40 parts by weight.
When the amount of the carbon black coat formed is not more than 10 part by weight, it is difficult to reduce the myristic acid-adsorption to not more than 0.3 mg/m2.
When the total amount of carbon black coat formed is more than 40 parts by weight, the myristic acid-adsorption of the obtained composite particles is as low as less than 0.01 mg/m2.
As the carbon black fine particles used in the present invention, there may be exemplified commercially available carbon blacks such as furnace black, channel black or the like. Specific examples of the commercially available carbon blacks usable in the present invention, may include #3050, #3150, #3250, #3750, #3950, MA100, MA7, #1000, #2400B, #30, MA77, MA8, #650, MA11, #50, #52, #45, #2200B, MA600, etc. (tradename, produced by MITSUBISHI CHEMICAL CORP.), SEAST 9H, SEAST 7H, SEAST 6, SEAST 3H, SEAST 300, SEAST FM, etc. (tradename, produced by TOKAI CARBON CO., LTD.), Raven 1250, Raven 860, Raven 1000, Raven 1190 ULTRA, etc. (tradename, produced by COLOMBIAN CHEMICALS COMPANY), Ketchen black EC, Ketchen black EC600JD, etc. (tradename, produced by KETCHEN INTERNATIONAL CO., LTD.), BLACK PEARLS-L, BLACK PEARLS 1000, BLACK PEARLS 4630, VULCAN XC72, REGAL 660, REGAL 400, etc. (tradename, produced by CABOTT SPECIALTY CHEMICALS INK CO., LTD.), or the like.
In the consideration of the reducing effect of the myristic acid-adsorption, the carbon black fine particles having a pH value of not more than 9.0 is preferred. Especially, there may be exemplified #3050, #3150, #3250, #3750, #3950, MA100, MA7, #1000, #2400B, #30, MA77, MA8, #650, MA11, #50, #52, #45, #2200B, MA600 (tradename, produced by MITSUBISHI CHEMICAL CORP.), SEAST 9H, SEAST 7H, SEAST 6, SEAST 3H, SEAST 300, SEAST FM (tradename, produced by TOKAI CARBON CO., LTD.), Raven 1250, Raven 860, Raven 1000, Raven 1190 ULTRA (tradename, produced by COLOMBIAN CHEMICALS COMPANY), BLACK PEARLS-L, BLACK PEARLS 1000, BLACK PEARLS 4630, REGAL 660, REGAL 400 (tradename, produced by CABOT SPECIALTY CHEMICALS INK CO., LTD.).
Further, in the consideration of more uniform coat of carbon black to the coating layer comprising at least one organosilicon compound, the carbon black fine particles having a DBP oil absorption of not more than 180 ml/100 g is preferred. Especially, there may be exemplified #3050, #3150, #3250, MA100, MA7, #1000, #2400B, #30, MA77, MA8, #650, MA11, #50, #52, #45, #2200B, MA600 (tradename, produced by MITSUBISHI CHEMICAL CORP.), SEAST 9H, SEAST 7H, SEAST 6, SEAST 3H, SEAST 300, SEAST FM (tradename, produced by TOKAI CARBON CO., LTD.), Raven 1250, Raven 860, Raven 1000, Raven 1190 ULTRA (tradename, produced by COLOMBIAN CHEMICALS COMPANY), BLACK PEARLS-L, BLACK PEARLS 1000, BLACK PEARLS 4630, REGAL 660, REGAL 400 (tradename, produced by CABOT SPECIALTY CHEMICALS INK CO., LTD.).
The thickness of carbon black coat is usually not more than 0.06 xcexcm, preferably not more than 0.04 xcexcm, more preferably not more than 0.03 xcexcm, still more preferably not more than 0.02 xcexcm.
The particle shape and size of the black magnetic acicular composite particles according to the present invention, are considerably varied depending upon those of the core particles. More specifically, the particle shape or configuration of the magnetic acicular composite particles is similar to that of the core particles, and the particle size of the magnetic acicular composite particles is slightly larger than that of the core particles.
That is, the black magnetic acicular composite particles according to the present invention, have an average major axial diameter of usually 0.051 to 0.35 xcexcm, preferably 0.051 to 0.34 xcexcm, more preferably 0.051 to 0.33 xcexcm; and an aspect ratio of usually 2.0:1 to 20.0:1, preferably 2.5:1 to 18.0:1, more preferably 3.0:1 to 15.0:1.
When the average major axial diameter is more than 0.35 xcexcm, the obtained black magnetic acicular composite particles become too large. In the case where such large particles are used, the obtained magnetic recording layer may tend to be deteriorated in surface smoothness of coating film. When the average major axial diameter is less than 0.051 xcexcm, the intermolecular force between the particles may become too large due to fineness thereof, so that the obtained composite particles may tend to be agglomerated together, resulting in deteriorated dispersibility in vehicle upon the production of a magnetic coating composition.
When the aspect ratio is more than 20.0:1, the particles may tend to be entangled or interlaced with each other, sometimes resulting in deteriorated dispersibility in vehicle upon the production of a magnetic coating composition and increased viscosity of the magnetic coating composition. When the aspect ratio is less than 2.0:1, the strength of coating film of the obtained magnetic recording medium using such particles may become small.
The geometrical standard deviation value of major axial diameters of the black magnetic acicular composite particles according to the present invention is usually not more than 2.0. When the geometrical standard deviation value is more than 2.0, coarse particles may be present in the obtained magnetic acicular composite particles, thereby adversely affecting the surface smoothness of the obtained coating film. In the consideration of the surface smoothness of coating film, the geometrical standard deviation value is preferably not more than 1.8, more preferably not more than 1.6. In the consideration of industrial productivity, the geometrical standard deviation value is not less than 1.01. Meanwhile, the particles having a geometrical standard deviation value of less than 1.01 are difficult to industrially produce.
The black magnetic acicular composite particles have a myristic acid absorption of usually 0.01 to 0.3 mg/m2, preferably 0.01 to 0.29 mg/m2, more preferably 0.01 to 0.28 mg/m2.
When the myristic acid-adsorption of the black magnetic acicular composite particles is within the above-specified range, the amount of myristic acid absorbed thereinto is adequate, so that the amount of myristic acid oozed onto the surface of the magnetic recording layer can be readily controlled to an appropriate level. As a result, upon the repeated use of magnetic tape, it is possible to maintain a sufficiently low friction coefficient of the magnetic tape for a long period of time, thereby ensuring an excellent running property thereof.
The black magnetic acicular composite particles according to the present invention have a BET specific surface area of preferably 21 to 160 m2/g, more preferably 26 to 130 m2/g, still more preferably 29 to 110 m2/g. When the BET specific surface area is less than 21 m2/g, the obtained black magnetic acicular composite particles may tend to become coarse or be sintered together. In the case where such particles are used to produce a magnetic recording layer, the obtained coating film may tend to be deteriorated in surface smoothness. When the BET specific surface area is more than 160 m2/g, the intermolecular force between the particles may be increased due to fineness thereof. As a result, the obtained particles may tend to be agglomerated together, resulting in deteriorated dispersibility in vehicle upon the production of magnetic coating composition.
As to the blackness of the black magnetic acicular composite particles having 0.5 to 10 parts by weight of the carbon black coat, the L* value thereof is usually not more than 23, preferably not more than 22, more preferably not more than 21. When the L* value is more than 23, the lightness of the particles becomes too high, thereby failing to obtain particles having a sufficient blackness. The L* value of the black magnetic acicular composite particles thereof is not less than 15.
As to the blackness of the black magnetic acicular particles, the L* value thereof is preferably not more than 22, more preferably not more than 21, still more preferably not more than 20. When the L* value is more than 22, the lightness of the particles becomes too high, thereby failing to obtain particles having a sufficient blackness. The L* value of the black magnetic acicular particles thereof is not less than 15.
The black magnetic acicular particles have a volume resistivity value of preferably not more than 1.0xc3x97106 xcexa9xc2x7cm, more preferably 1.0xc3x97103 to 5.0xc3x97105 xcexa9xc2x7cm, still more preferably 1.0xc3x97103 to 1.0xc3x97105 xcexa9xc2x7cm. When the volume resistivity value is more than 1.0xc3x97106 xcexa9xc2x7cm, it is difficult to sufficiently reduce the surface electrical resistivity value of the obtained magnetic recording medium.
The carbon black desorption percentage of the black magnetic acicular composite particles is preferably not more than 20%, more preferably not more than 10%. When the carbon black desorption percentage is more than 20%, the obtained particles may tend to be inhibited from uniformly dispersed in vehicle due to desorbed and liberated carbon black upon the production of magnetic recording media.
As to magnetic properties of the black magnetic acicular composite particles according to the present invention, the coercive force value thereof is usually 500 to 3500 Oe (39.8 to 278.5 kA/m), the saturation magnetization value is usually 60 to 170 emu/g (60 to 170 Am2/kg).
In the case where the magnetic acicular cobalt-coated iron oxide particles are used as the core particles, the coercive force value thereof is preferably 500 to 1,700 Oe (39.8 to 135.3 kA/m), more preferably 550 to 1,700 Oe (43.8 to 135.3 kA/m); and the saturation magnetization value thereof is preferably 60 to 90 emu/g (60 to 90 Am2/kg), more preferably 65 to 90 emu/g (65 to 90 Am2/kg).
In the case where the magnetic acicular metal particles containing iron as a main component are used as the core particles, the coercive force value thereof is preferably 800 to 3,500 Oe (63.7 to 278.5 kA/m), more preferably 900 to 3,500 Oe (71.6 to 278.5 kA/m); and the saturation magnetization value thereof is preferably 90 to 170 emu/g (90 to 170 Am2/kg), more preferably 100 to 170 emu/g (100 to 170 Am2/kg).
At least a part of the surface of the magnetic acicular particle as a core particle used in the present invention may be coated with at least one selected from the group consisting of a hydroxide of aluminum, an oxide of aluminum, a hydroxide of silicon and an oxide of silicon (hereinafter referred to as xe2x80x9chydroxides and/or oxides of aluminum and/or siliconxe2x80x9d). When the black magnetic acicular composite particles obtained by using as core particles the magnetic acicular particles which are coated with the hydroxides and/or oxides of aluminum and/or silicon, are dispersed in a vehicle, since it is possible to more effectively reduce the carbon black desorption percentage, it is more easy to obtain a desired dispersibility.
The amount of the hydroxides and/or oxides of aluminum and/or silicon coat is usually not more than 20% by weight, preferably 0.01 to 20% by weight (calculated as Al and/or SiO2) based on the total weight of the magnetic acicular particles coated. If it is less than 0.01% by weight (calculated as Al and/or SiO2) based on the total weight of the magnetic acicular particles coated, the dispersibility-improving effect by coating therewith may be insufficient.
When the coating amount of the hydroxide of aluminum or the like is more than 20% by weight, although there can be obtained a sufficient effect of reducing the percentage of carbon black desorbed or fallen-off from the surfaces of the core particles, the effect is already saturated and, therefore, the use of such a large coating amount of the hydroxide of aluminum or the like is unnecessary and meaningless.
From the point of view of dispersibility in the vehicle and industrial productivity, the more preferable amount of coating composition is 0.05 to 10% by weight (calculated as Al and/or SiO2) based on the total weight of the magnetic acicular particles coated.
The particle size, geometrical standard deviation value, BET specific surface area, blackness L* value, volume resistivity and magnetic properties of the black magnetic acicular composite particles wherein the surface of the core particle is coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, are substantially the same as those of the black magnetic acicular composite particles wherein the core particle is uncoated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention.
In addition, the desorption percentage of carbon black of the black magnetic acicular composite particles wherein the surface of the core particle is coated with the hydroxides and/or oxides of aluminum and/or silicon is more improved as compared with that of the black magnetic acicular composite particles wherein the core particle is uncoated therewith. The carbon black desorption percentage of the black magnetic acicular composite particles wherein the surface of the core particle is coated with the hydroxides and/or oxides of aluminum and/or silicon, is preferably not more than 10%, more preferably not more than 5%.
Next, the magnetic recording medium of the first and second aspect in the present invention is described.
The magnetic recording medium according to the present invention comprises:
a non-magnetic base film; and
a magnetic recording layer formed on the non-magnetic base film, comprising a binder resin and the black magnetic acicular composite particles.
As the non-magnetic base film, the following materials which are at present generally used for the production of a magnetic recording medium are usable as a raw material: a synthetic resin such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, polyamide, polyamideimide and polyimide; foil and plate of a metal such as aluminum and stainless steel; and various kinds of paper. The thickness of the non-magnetic base film varies depending upon the material, but it is usually about 1.0 to 300 xcexcm, preferably 2.0 to 200 xcexcm.
In the case of a magnetic disc, polyethylene terephthalate is usually used as the non-magnetic base film, and the thickness thereof is usually 50 to 300 xcexcm, preferably 60 to 200 xcexcm.
In a magnetic tape, when polyethylene terephthalate is used as the non-magnetic base film, the thickness thereof is usually 3 to 100 xcexcm, preferably 4 to 20 xcexcm; when polyethylene naphthalate is used, the thickness thereof is usually 3 to 50 xcexcm, preferably 4 to 20 xcexcm; and when polyamide is used, the thickness thereof is usually 2 to 10 xcexcm, preferably 3 to 7 xcexcm.
As the binder resin used in the present invention, the following resins which are at present generally used for the production of a magnetic recording medium are usable: vinyl chloride-vinyl acetate copolymer, polyurethane resin, vinyl chloride-vinyl acetate-maleic acid copolymer, urethane elastomer, butadiene-acrylonitrile copolymer, polyvinyl butyral, cellulose derivative such as nitrocellulose, polyester resin, synthetic rubber resin such as polybutadiene, epoxy resin, polyamide resin, polyisocyanate, electron radiation curing acryl urethane resin and mixtures thereof.
Each of these resin binders may contain a functional group such as xe2x80x94OH, xe2x80x94COOH, xe2x80x94SO3M, xe2x80x94OPO2M2 and xe2x80x94NH2, wherein M represents H, Na or K. With the consideration of the dispersibility of the black magnetic acicular composite particles, a binder resin containing a functional group xe2x80x94COOH or xe2x80x94SO3M is preferable.
The thickness of the magnetic recording layer obtained by applying the magnetic coating composition on the surface of the non-magnetic base film and dried, is usually in the range of 0.01 to 5.0 xcexcm. If the thickness is less than 0.01 xcexcm, uniform coating may be difficult, so that unfavorable phenomenon such as unevenness on the coating surface is observed. On the other hand, when the thickness exceeds 5.0 xcexcm, it may be difficult to obtain desired signal recording property due to an influence of diamagnetism. The preferable thickness is in the range of 0.1 to 4.0 xcexcm.
The mixing ratio of the black magnetic acicular composite particles with the binder resin is usually 5 to 2000 parts by weight, preferably 100 to 1000 parts by weight based on 100 parts by weight of the binder resin.
When the amount of the black magnetic acicular composite particles blended is less than 5 parts by weight, the obtained magnetic coating composition contains a too small amount of the black magnetic acicular composite particles. As a result, when a coating film is produced from such a magnetic coating composition, it is not possible to obtain a coating film in which the black magnetic acicular composite particles are continuously dispersed, so that the surface smoothness and the strength of the coating film become unsatisfactory. On the other hand, when the amount of the black magnetic acicular composite particles blended is more than 2,000 parts by weight, the amount of the black magnetic acicular composite particles becomes too large relative to that of the binder resin, so that it is not possible to sufficiently disperse the black magnetic acicular composite particles in the magnetic coating composition. As a result, when a coating film is produced from such a magnetic coating composition, it is difficult to obtain a coating film having a sufficiently smooth surface. Further, since the black magnetic acicular composite particles cannot be sufficiently bound with each other by the binder resin, the obtained coating film tends to become brittle.
In the magnetic recording medium according to the present invention, the amount of carbon black fine particles added to the magnetic recording layer thereof can be reduced to usually less than 6 parts by weight, preferably less than 5 parts by weight, more preferably less than 3 parts by weight based on 100 parts by weight of the black magnetic acicular composite particles.
Further, in the case where the black magnetic acicular composite particles wherein a large amount of the carbon black can be coated onto the surface thereof, are used as magnetic particles, it can be expected to omit the addition of the carbon black fine particles to the magnetic recording layer.
Incidentally, the magnetic recording layer may optionally contain a lubricant, an abrasive, an anti-static agent and other additives which are usually used for the production of magnetic recording media, in an amount of 0.1 to 50 parts by weight based on 100 parts of the binder resin.
The magnetic recording medium of the third and fourth aspects in the present invention, comprises a non-magnetic base film, a non-magnetic undercoat layer formed on the non-magnetic base film comprising a binder resin and non-magnetic particles, and a magnetic recording layer formed on the non-magnetic undercoat layer, comprising a binder resin and black magnetic acicular composite particles.
The thickness of the non-magnetic undercoat layer is preferably 0.2 to 10.0 xcexcm. When the thickness of the non-magnetic undercoat layer is less than 0.2 xcexcm, it may be difficult to improve the surface roughness of the non-magnetic substrate, and the stiffness of a coating film formed thereon tends to be unsatisfactory. In the consideration of reduction in total thickness of the magnetic recording medium as well as the stiffness of the coating film, the thickness of the non-magnetic undercoat layer is more preferably in the range of 0.5 to 5.0 xcexcm.
As the binder resin, the same binder resin as that used for the production of the magnetic recording layer is usable.
The mixing ratio of the non-magnetic particles to the binder resin is usually 5 to 2000 parts by weight, preferably 100 to 1000 parts by weight based on 100 parts by weight of the binder resin.
When the content of the non-magnetic particles is as small as less than 5 parts by weight, such a non-magnetic undercoat layer in which the non-magnetic particles are uniformly and continuously dispersed may not be obtained upon coating, resulting in insufficient surface smoothness and insufficient stiffness of the non-magnetic substrate. When the content of the non-magnetic particles is more than 2,000 parts by weight, the non-magnetic particles may not be sufficiently dispersed in a non-magnetic coating composition since the amount of the non-magnetic particles is too large as compared to that of the binder resin. As a result, when such a non-magnetic coating composition is coated onto the non-magnetic base film, it may become difficult to obtain a coating film having a sufficiently smooth surface. Further, since the non-magnetic particles may not be sufficiently bonded together through the binder resin, the obtained coating film tends to become brittle.
It is possible to add an additive such as a lubricant, a polishing agent, an antistatic agent, etc. which are generally used for the production of a magnetic recording medium, to the non-magnetic undercoating layer. The mixing ratio of the additive to the binder resin is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the binder resin.
As the non-magnetic particles used in the non-magnetic undercoat layer of the present invention, there may be exemplified non-magnetic inorganic particles ordinarily used for forming a non-magnetic undercoat layer in conventional magnetic recording media. Specific examples of the non-magnetic particles may include hematite particles, iron oxide hydroxide particles, titanium oxide particles, zinc oxide particles, tin oxide particles, tungsten oxide particles, silicon dioxide particles, xcex1-alumina particles, xcex2-alumina particles, xcex3-alumina particles, chromium oxide particles, cerium oxide particles, silicon carbide particles, titanium carbide particles, silicon nitride particles, boron nitride particles, calcium carbonate particles, barium carbonate particles, magnesium carbonate particles, strontium carbonate particles, calcium sulfate particles, barium sulfate particles, molybdenum disulfide particles, barium titanate particles or the like. These non-magnetic particles may be used singly or in the form of a mixture of any two or more thereof. Among them, the use of hematite particles, iron oxide hydroxide particles, titanium oxide particles and the like is preferred.
In the present invention, in order to improve the dispersibility of the non-magnetic particles in vehicle upon the production of non-magnetic coating composition, the non-magnetic particles may be surface-treated with hydroxides of aluminum, oxides of aluminum, hydroxides of silicon, oxides of silicon or the like to form a coat made of any of these compounds on the surfaces thereof. Further, the non-magnetic particles may contain Al, Ti, Zr, Mn, Sn, Sb or the like inside thereof, if required, in order to improve various properties of the obtained magnetic recording media such as light transmittance, surface electrical resistivity, mechanical strength, surface smoothness, durability or the like.
The particle shape of the hematite particles as the core particles may include a granular shape such as a spherical shape, an irregular (anisotropic) shape, an octahedral shape, a hexahedral shape, a polyhedral shape or the like; an acicular shape such as a needle shape, a spindle shape, a rice ball shape or the like; and a plate shape, or the like.
The lower limit of the average particle size of the hematite particles as the core particles is usually 0.075 xcexcm, preferably 0.085 xcexcm, more preferably 0.095 xcexcm, and the upper limit thereof is usually 0.95 xcexcm, preferably 0.65xcexcm, more preferably 0.45 xcexcm.
(i) In the case where the shape of the core particles is granular-shaped, the lower limit of the average particle diameter of the granular-shaped hematite particles is usually 0.075 xcexcm, preferably 0.085 xcexcm, more preferably 0.095 xcexcm, and the upper limit thereof is usually 0.95 xcexcm, preferably 0.65 xcexcm, more preferably 0.45 xcexcm.
(ii) In the case where the shape of the core particles is acicular-shaped, the lower limit of the average particle diameter (average major axis diameter) of the acicular-shaped hematite particles is usually 0.075 xcexcm, preferably 0.085 xcexcm, more preferably 0.095 xcexcm, and the upper limit thereof is usually 0.95 xcexcm, preferably 0.65 xcexcm, more preferably 0.45 xcexcm; and the lower limit of the aspect ratio (average major axis diameter/average minor axis diameter) of the acicular-shaped hematite particles is usually 2:1, preferably 2.5:1, more preferably 3:1, and the upper limit thereof is usually 20:1, preferably 15:1, more preferably 10:1.
(iii) In the case where the shape of the core particles is plate-shaped, the lower limit of the average particle diameter (average plate surface diameter) of the plate-shaped hematite particles is usually 0.075 xcexcm, preferably 0.085 xcexcm, more preferably 0.095 xcexcm, and the upper limit thereof is usually 0.95 xcexcm, preferably 0.65 xcexcm, more preferably 0.45 xcexcm; and the lower limit of the plate ratio (average plate surface diameter/average thickness) of the plate-shaped hematite particles is usually 2:1, preferably 2.5:1, more preferably 3:1, and the upper limit thereof is usually 50:1, preferably 45:1, more preferably 40:1.
The magnetic recording medium according to the present invention has a coercive force of usually 500 to 3500 Oe (39.8 to 278.5 kA/m); a squareness (residual magnetic flux density Br/saturation magnetic flux density Bm) of usually 0.85 to 0.95; a gloss (of the coating film) of usually 165 to 300%; a surface roughness Ra (of the coating film) of usually not more than 11.5 nm; a Young""s modulus (relative value to a commercially available video tape: AV T-120 produced by Victor Company of Japan, Limited) of usually 124 to 160; a linear adsorption coefficient (of the coating film) of usually 1.75 to 10.00 xcexcmxe2x88x921; a surface electrical resistivity of usually not more than 1.0xc3x97108 xcexa9/cm2; a running durability time thereof of usually not less than 24 minutes.
The properties of the magnetic recording media of the first and second aspects are generally comprise: a non-magnetic base film and a magnetic recording layer formed on the non-magnetic base film.
In case of using the black magnetic acicular composite particles, wherein the magnetic acicular cobalt-coated iron oxide particles are used as core particles, which are coated with no hydroxides and/or oxides of aluminum and/or silicon, the magnetic recording medium of the first aspect in the present invention has a coercive force of usually 500 to 1,700 Oe (39.8 to 135.3 kA/m), preferably 550 to 1,700 Oe (43.8 to 135.3 kA/m); a squareness (residual magnetic flux density Br/saturation magnetic flux density Bm) of usually 0.85 to 0.95, preferably 0.86 to 0.95; a gloss (of the coating film) of usually 165 to 300%, preferably 170 to 300%; a surface roughness Ra (of the coating film) of usually not more than 11.5 nm, preferably 2.0 to 10.5 nm, more preferably 2.0 to 9.5 nm, a Young""s modulus (relative value to a commercially available video tape: AV T-120 produced by Victor Company of Japan, Limited) of usually 124 to 160, preferably 125 to 160; a linear adsorption coefficient (of the coating film) of usually 1.75 to 10.0 xcexcmxe2x88x921, preferably 1.80 to 10.0 xcexcmxe2x88x921; and a surface electrical resistivity of usually not more than 1.0xc3x97108 xcexa9/cm2, preferably not more than 7.5xc3x97107 xcexa9/cm2, more preferably not more than 5.0xc3x97107 xcexa9/cm2; a running durability time thereof of usually not less than 24 minutes, preferably not less than 25 minutes; a friction coefficient of usually 0.25 to 0.30, preferably 0.25 to 0.29.
In case of using the black magnetic acicular composite particles, wherein the magnetic acicular metal particles containing iron as a main component are used as core particles which are coated with no hydroxides and/or oxides of aluminum and/or silicon, the magnetic recording medium of the first aspect in the present invention has a coercive force of usually 800 to 3,500 Oe (63.7 to 278.5 kA/m), preferably 900 to 3,500 Oe (71.6 to 278.5 kA/m); a squareness (residual magnetic flux density Br/saturation magnetic flux density Bm) of usually 0.85 to 0.95, preferably 0.86 to 0.95; a gloss (of the coating film) of usually 185 to 300%, preferably 195 to 300%; a surface roughness Ra (of the coating film) of usually not more than 11.5 nm, preferably 2.0 to 10.5 nm, more preferably 2.0 to 9.5 nm, a Young""s modulus (relative value to a commercially available video tape: AV T-120 produced by Victor Company of Japan, Limited) of usually 124 to 160, preferably 125 to 160; a linear adsorption coefficient (of the coating film) of usually 1.85 to 10.0 xcexcmxe2x88x921, preferably 1.90 to 10.0 xcexcmxe2x88x921; and a surface electrical resistivity of usually not more than 1.0xc3x97108 xcexa9/cm2, preferably not more than 7.5xc3x97107 xcexa9/cm2, more preferably not more than 5.0xc3x97107 xcexa9/cm2; a running durability time thereof of usually not less than 24 minutes, preferably not less than 25 minutes; a friction coefficient of usually 0.25 to 0.30, preferably 0.25 to 0.29.
In case of using the black magnetic acicular composite particles, wherein the magnetic acicular cobalt-coated iron oxide particles as core particles which are coated with hydroxides and/or oxides of aluminum and/or silicon, the magnetic recording medium of the second aspect in the present invention has a coercive force of usually 500 to 1,700 Oe (39.8 to 135.3 kA/m), preferably 550 to 1,700 Oe (43.8 to 135.3 kA/m); a squareness (residual magnetic flux density Br/saturation magnetic flux density Bm) of usually 0.85 to 0.95, preferably 0.86 to 0.95; a gloss (of the coating film) of usually 170 to 300%, preferably 175 to 300%; a surface roughness Ra (of the coating film) of usually not more than 10.5 nm, preferably 2.0 to 9.5 nm, more preferably 2.0 to 8.5 nm, a Young""s modulus (relative value to a commercially available video tape: AV T-120 produced by Victor Company of Japan, Limited) of usually 126 to 160, preferably 127 to 160; a linear adsorption coefficient (of the coating film) of usually 1.75 to 10.0 xcexcmxe2x88x921, preferably 1.80 to 10.0 xcexcmxe2x88x921; and a surface electrical resistivity of usually not more than 1.0xc3x97108 xcexa9/cm2, preferably not more than 7.5xc3x97107 xcexa9/cm2, more preferably not more than 5.0xc3x97107 xcexa9/cm2; a running durability time thereof of usually not less than 26 minutes, preferably not less than 27 minutes; a friction coefficient of usually 0.21 to 0.26, preferably 0.21 to 0.25.
In case of using the black magnetic acicular composite particles, wherein the magnetic acicular metal particles containing iron as a main component as core particles which are coated with hydroxides and/or oxides of aluminum and/or silicon, the magnetic recording medium the second aspect in the present invention has a coercive force of usually 800 to 3500 Oe (63.7 to 278.5 kA/m), preferably 900 to 3500 Oe (71.6 to 278.5 kA/m); a squareness (residual magnetic flux density Br/saturation magnetic flux density Bm) of usually 0.85 to 0.95, preferably 0.86 to 0.95; a gloss (of the coating film) of usually 190 to 300%, preferably 200 to 300%; a surface roughness Ra (of the coating film) of usually not more than 10.5 nm, preferably 2.0 to 9.5 nm, more preferably 2.0 to 8.5 nm, a Young""s modulus (relative value to a commercially available video tape: AV T-120 produced by Victor Company of Japan, Limited) of usually 126 to 160, preferably 127 to 160; a linear adsorption coefficient (of the coating film) of usually 1.85 to 10.0 xcexcmxe2x88x921, preferably 1.90 to 10.0 xcexcmxe2x88x921; and a surface electrical resistivity of usually not more than 1.0xc3x97108 xcexa9/cm2, preferably not more than 7.5xc3x97107 xcexa9/cm2, more preferably not more than 5.0xc3x97107 xcexa9/cm2; a running durability time thereof of usually not less than 26 minutes, preferably not less than 27 minutes; a friction coefficient of usually 0.21 to 0.26, preferably 0.21 to 0.25.
The properties of the magnetic recording media of the third and fourth aspect are generally comprise: a non-magnetic base film, a non-magnetic undercoat layer formed on the non-magnetic base film, and a magnetic recording layer formed on the non-magnetic undercoat layer.
In case of using the black magnetic acicular composite particles, wherein the magnetic acicular cobalt-coated iron oxide particles which are coated with no hydroxides and/or oxides of aluminum and/or silicon, the magnetic recording medium the fifth aspect the present invention has a coercive force of usually 500 to 1,700 Oe (39.8 to 135.3 kA/m), preferably 550 to 1,700 Oe (43.8 to 135.3 kA/m); a squareness (residual magnetic flux density Br/saturation magnetic flux density Bm) of usually 0.85 to 0.95, preferably 0.86 to 0.95; a gloss (of the coating film) of usually 165 to 300%, preferably 170 to 300%; a surface roughness Ra (of the coating film) of usually not more than 11.0 nm, preferably 2.0 to 10.5 nm, more preferably 2.0 to 10.0 nm, a Young""s modulus (relative value to a commercially available video tape: AV T-120 produced by Victor Company of Japan, Limited) of usually 125 to 160, preferably 126 to 160; a linear adsorption coefficient (of the coating film) of usually 1.40 to 10.0 xcexcmxe2x88x921, preferably 1.45 to 10.0 xcexcmxe2x88x921; and a surface electrical resistivity of usually not more than 1.0xc3x97109 xcexa9/cm2, preferably not more than 7.5xc3x97108 xcexa9/cm2, more preferably not more than 5.0xc3x97108 xcexa9/cm2; a running durability time thereof of usually not less than 25 minutes, preferably not less than 26 minutes.
In case of using the black magnetic acicular composite particles wherein the magnetic acicular cobalt-coated iron oxide particles which are coated with no hydroxides and/or oxides of aluminum and/or silicon, the magnetic recording medium of the third aspect not only can satisfy the above described properties, but also can exhibit a linear absorption (of coating film) of usually 1.80 to 10.00 xcexcmxe2x88x921, preferably 1.85 to 10.00 xcexcmxe2x88x921; a surface electrical resistivity value (of coating film) of usually not more than 1.0xc3x97108 xcexa9/cm2, preferably not more than 7.5xc3x97107 xcexa9/cm2, more preferably not more than 5.0xc3x97107 xcexa9/cm2; a friction coefficient of usually 0.25 to 0.30, preferably 0.25 to 0.29; and a running durability time thereof of usually not less than 26 minutes, preferably not less than 27 minutes.
In case of using the black magnetic acicular composite particles, wherein the magnetic acicular metal particles containing iron as a main component which are coated with no hydroxides and/or oxides of aluminum and/or silicon, the magnetic recording medium the fifth aspect in the present invention has a coercive force of usually 800 to 3,500 Oe (63.7 to 278.5 kA/m), preferably 900 to 3,500 Oe (71.6 to 278.5 kA/m); a squareness (residual magnetic flux density Br/saturation magnetic flux density Bm) of usually 0.85 to 0.95, preferably 0.86 to 0.95; a gloss (of the coating film) of usually 185 to 300%, preferably 195 to 300%; a surface roughness Ra (of the coating film) of usually not more than 11.0 nm, preferably 2.0 to 10.5 nm, more preferably 2.0 to 10.0 nm, a Young""s modulus (relative value to a commercially available video tape: AV T-120 produced by Victor Company of Japan, Limited) of usually 125 to 160, preferably 126 to 160; a linear adsorption coefficient (of the coating film) of usually 1.40 to 10.0 xcexcmxe2x88x921, preferably 1.45 to 10.0 xcexcmxe2x88x921; and a surface electrical resistivity of usually not more than 1.0xc3x97109 xcexa9/cm2, preferably not more than 7.5xc3x97108 xcexa9/cm2, more preferably not more than 5.0xc3x97108 xcexa9/cm2; a running durability time thereof of usually not less than 25 minutes, preferably not less than 26 minutes.
In case of using the black magnetic acicular composite particles, wherein the magnetic acicular metal particles containing iron as a main component which are coated with hydroxides and/or oxides of aluminum and/or silicon, the magnetic recording medium of the third aspect not only can satisfy the above described properties, but also can exhibit a linear absorption (of coating film) of usually 1.80 to 10.00 xcexcmxe2x88x921, preferably 1.85 to 10.00 xcexcmxe2x88x921; a surface electrical resistivity value (of coating film) of usually not more than 1.0xc3x97108 xcexa9/cm2, preferably not more than 7.5xc3x97107 xcexa9/cm2, more preferably not more than 5.0xc3x97107 xcexa9/cm2; a friction coefficient of usually 0.25 to 0.30, preferably 0.25 to 0.29; and a running durability time thereof of usually not less than 26 minutes, preferably not less than 27 minutes.
In case of using the black magnetic acicular composite particles, wherein the magnetic acicular cobalt-coated iron oxide particles which are coated with hydroxides and/or oxides of aluminum and/or silicon, the magnetic recording medium of the sixth aspect in the present invention has a coercive force of usually 500 to 1,700 Oe (39.8 to 135.3 kA/m), preferably 550 to 1,700 Oe (43.8 to 135.3 kA/m); a squareness (residual magnetic flux density Br/saturation magnetic flux density Bm) of usually 0.85 to 0.95, preferably 0.86 to 0.95; a gloss (of the coating film) of usually 170 to 300%, preferably 175 to 300%; a surface roughness Ra (of the coating film) of usually not more than 10.0 nm, preferably 2.0 to 9.5 nm, more preferably 2.0 to 9.0 nm, a Young""s modulus (relative value to a commercially available video tape: AV T-120 produced by Victor Company of Japan, Limited) of usually 127 to 160, preferably 128 to 160; a linear adsorption coefficient (of the coating film) of usually 1.45 to 10.0 xcexcmxe2x88x92, preferably 1.50 to 10.0 xcexcmxe2x88x921; and a surface electrical resistivity of usually not more than 1.0xc3x97109 xcexa9/cm2, preferably not more than 7.5xc3x97108 xcexa9/cm2, more preferably not more than 5.0xc3x97108 xcexa9/cm2; a running durability time thereof of usually not less than 26 minutes, preferably not less than 27 minutes.
In case of using the black magnetic acicular composite particles, wherein the magnetic acicular cobalt-coated iron oxide particles which are coated with hydroxides and/or oxides of aluminum and/or silicon, the magnetic recording medium of the fourth aspect not only can satisfy the above described properties, but also can exhibit a linear absorption (of coating film) of usually 1.85 to 10.00 xcexcmxe2x88x921, preferably 1.90 to 10.00 xcexcmxe2x88x921; a surface electrical resistivity value (of coating film) of usually not more than 5.0xc3x97107 xcexa9/cm2, preferably not more than 2.5xc3x97107 xcexa9/cm2, more preferably not more than 1.0xc3x97107 xcexa9/cm2; a friction coefficient of usually 0.21 to 0.26, preferably 0.21 to 0.25; and a running durability time thereof of usually not less than 27 minutes, preferably not less than 28 minutes.
In case of using the black magnetic acicular composite particles, wherein the magnetic acicular metal particles containing iron as a main component which are coated with hydroxides and/or oxides of aluminum and/or silicon, the magnetic recording medium the sixth aspect in the present invention has a coercive force of usually 800 to 3,500 Oe (63.7 to 278.5 kA/m), preferably 900 to 3,500 Oe (71.6 to 278.5 kA/m); a squareness (residual magnetic flux density Br/saturation magnetic flux density Bm) of usually 0.85 to 0.95, preferably 0.86 to 0.95; a gloss (of the coating film) of usually 190 to 300%, preferably 200 to 300%; a surface roughness Ra (of the coating film) of usually not more than 10.0 nm, preferably 2.0 to 9.5 nm, more preferably 2.0 to 9.0 nm, a Young""s modulus (relative value to a commercially available video tape: AV T-120 produced by Victor Company of Japan, Limited) of usually 127 to 160, preferably 128 to 160; a linear adsorption coefficient (of the coating film) of usually 1.45 to 10.0 xcexcmxe2x88x921, preferably 1.50 to 10.0 xcexcmxe2x88x921; and a surface electrical resistivity of usually not more than 1.0xc3x97109 xcexa9/cm2, preferably not more than 7.5xc3x97108 xcexa9/cm2, more preferably not more than 5.0xc3x97108 xcexa9/cm2; a running durability time thereof of usually not less than 26 minutes, preferably not less than 27 minutes.
In case of using the black magnetic acicular composite particles, wherein the magnetic acicular metal particles containing iron as a main component which are coated with hydroxides and/or oxides of aluminum and/or silicon, the magnetic recording medium of the fourth aspect not only can satisfy the above described properties, but also can exhibit a linear absorption (of coating film) of usually 1.85 to 10.00 xcexcmxe2x88x921, preferably 1.90 to 10.00 xcexcmxe2x88x921; a surface electrical resistivity value (of coating film) of usually not more than 5.0xc3x97107 xcexa9/cm2, preferably not more than 2.5xc3x97107 xcexa9/cm2, more preferably not more than 1.0xc3x97107 xcexa9/cm2; a friction coefficient of usually 0.21 to 0.26, preferably 0.21 to 0.25; and a running durability time thereof of usually not less than 27 minutes, preferably not less than 28 minutes.
The black magnetic acicular composite particles according to the present invention can be produced by the following method.
As the core particles used in the present invention, known Co-coated magnetic acicular iron oxide particles and magnetic acicular metal particles containing iron as a main component may be used.
The coating of the magnetic acicular particles with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes, may be conducted (i) by mechanically mixing and stirring the magnetic acicular particles together with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes; or (ii) by mechanically mixing and stirring both the components together while spraying the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes onto the magnetic acicular particles. In these cases, substantially whole amount of the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes added can be applied onto the surfaces of the magnetic acicular particles.
In addition, by conducting the above-mentioned mixing or stirring treatment (i) of the hematite particles as core particles together with the alkoxysilane compounds, at least a part of the alkoxysilane compounds coated on the hematite particles as core particles may be changed to the organosilane compounds. In this case, there is also no affection against the formation of the carbon black coat thereon.
In order to uniformly coat the surfaces of the magnetic acicular particles with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes, it is preferred that the magnetic acicular particles are preliminarily diaggregated by using a pulverizer.
As apparatus (a) for mixing and stirring treatment (i) of the core particles with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes to form the coating layer thereof, and as apparatus (b) for mixing and stirring treatment (ii) of carbon black fine particles with the particles whose surfaces are coated with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes to form the carbon black coat, there may be preferably used those apparatus capable of applying a shear force to the particles, more preferably those apparatuses capable of conducting the application of shear force, spaturate force and compressed force at the same time. In addition, by conducting the above mixing or stirring treatment (a) of the core particles together with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes, at least a part of the alkoxysilane compounds coated on the core particles may be changed to the organosilane compounds.
As such apparatuses, there may be exemplified wheel-type kneaders, ball-type kneaders, blade-type kneaders, roll-type kneaders or the like. Among them, wheel-type kneaders are preferred.
Specific examples of the wheel-type kneaders may include an edge runner (equal to a mix muller, a Simpson mill or a sand mill), a multi-mull, a Stotz mill, a wet pan mill, a Conner mill, a ring muller, or the like. Among them, an edge runner, a multi-mull, a Stotz mill, a wet pan mill and a ring muller are preferred, and an edge runner is more preferred.
Specific examples of the ball-type kneaders may include a vibrating mill or the like. Specific examples of the blade-type kneaders may include a Henschel mixer, a planetary mixer, a Nawter mixer or the like. Specific examples of the roll-type kneaders may include an extruder or the like.
In order to coat the surfaces of the core particles with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes as uniformly as possible, the conditions of the above mixing or stirring treatment may be appropriately controlled such that the linear load is usually 2 to 200 Kg/cm (19.6 to 1960 N/cm), preferably 10 to 150 Kg/cm (98 to 1470 N/cm), more preferably 15 to 100 Kg/cm (147 to 980 N/cm); and the treating time is usually 5 to 120 minutes, preferably 10 to 90 minutes. It is preferred to appropriately adjust the stirring speed in the range of usually 2 to 2,000 rpm, preferably 5 to 1,000 rpm, more preferably 10 to 800 rpm.
The amount of the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes added, is preferably 0.15 to 45 parts by weight based on 100 parts by weight of the magnetic acicular particles.
Next, the carbon black fine particles are added to the magnetic acicular particles coated with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes or the terminal-modified polysiloxanes, and the resultant mixture is mixed and stirred to form a carbon black coat (single carbon black coat) on the surfaces of the coating layer composed of the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes or the terminal-modified polysiloxanes.
It is preferred that the carbon black fine particles are added little by little and slowly, especially, preferably 5 minutes to 24 hours, more preferably 5 minutes to 20 hours.
In order to form a single carbon black coat (carbon black-coating monolayer) onto the coating layer composed of the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes as uniformly as possible, the conditions of the above mixing or stirring treatment can be appropriately controlled such that the linear load is usually 2 to 200 Kg/cm (19.6 to 1960 N/cm), preferably 10 to 150 Kg/cm (98 to 1470 N/cm), more preferably 15 to 100 Kg/cm (147 to 980 N/cm); and the treating time is usually 5 to 120 minutes, preferably 10 to 90 minutes. It is preferred to appropriately adjust the stirring speed in the range of usually 2 to 2,000 rpm, preferably 5 to 1,000 rpm, more preferably 10 to 800 rpm.
The amount of carbon black fine particles added is from more than 10 parts by weight to 40 parts by weight based on 100 parts by weight of the core particles. When the amount of carbon black fine particles added is not more than 10 part by weight, the amount of carbon black coat may become too small. As a result, it may be difficult to obtain black magnetic acicular composite particles having an excellent blackness and a low volume resistivity value. When the amount of carbon black fine particles added is more than 40 parts by weight, the effect of improving the blackness and the volume resistivity value of the obtained black magnetic acicular composite particles is already saturated and, therefore, the addition of such a large amount of carbon black fine particles is unnecessary and meaningless.
In particular, in order to obtain black magnetic acicular composite particles having a carbon black coat, it is preferred to add carbon black in two or more separate parts while alternately repeating the addition and adhesion thereof.
In the present invention, after carbon black is adhered onto the core particles, the obtained black magnetic acicular composite particles may be dried or heat-treated. The temperature used in the drying or heat-treatment, is preferably 40 to 200xc2x0 C., more preferably 60 to 150xc2x0 C., and the heating time is preferably from 10 minutes to 12 hours, more preferably from 30 minutes to 3 hours. By conducting such drying or heat-treatment, the alkoxysilane can be converted into organosilane compounds.
The alkoxysilane used to coat the core particles in the thus obtained composite particles is finally converted into the organosilane compound through these steps.
It is preferred that the cobalt-coated magnetite particles, the magnetic acicular metal particles containing iron as a main component, the magnetic acicular iron alloy particles or the like, which are susceptible to oxidation, be placed within a mixing device and purged with an inert gas such as N2 gas in order to prevent the deterioration in magnetic properties thereof by the oxidation.
At least a part of the surface of the magnetic acicular particles may be coated with at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon (hereinafter referred to as xe2x80x9chydroxides and/or oxides of aluminum and/or siliconxe2x80x9d), if required, in advance of mixing and stirring with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, or the terminal-modified polysiloxanes.
The coating of the hydroxides and/or oxides of aluminum and/or silicon may be conducted by adding an aluminum compound, a silicon compound or both the compounds to a water suspension in which the magnetic acicular particles are dispersed, followed by mixing and stirring, and further adjusting the pH value of the suspension, if required, thereby coating the surfaces of the magnetic acicular particles with at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon. The thus obtained magnetic acicular particles coated with the hydroxides and/or oxides of aluminum and/or silicon are then filtered out, washed with water, dried and pulverized. Further, the particles coated with the hydroxides and/or oxides of aluminum and/or silicon may be subjected to post-treatments such as deaeration treatment and compaction treatment, if required.
As the aluminum compounds, there may be exemplified aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride or aluminum nitrate, alkali aluminates such as sodium aluminate or the like.
The amount of the aluminum compound added is 0.01 to 20% by weight (calculated as Al) based on the weight of the magnetic acicular particles. When the amount of the aluminum compound added is less than 0.01% by weight, it may be difficult to sufficiently coat the surfaces of the magnetic acicular particles with hydroxides and/or oxides of aluminum, thereby failing to improve the effective reduction of the carbon black desorption percentage. On the other hand, when the amount of the aluminum compound added is more than 20% by weight, the coating effect is saturated and, therefore, it is meaningless to add such an excess amount of the aluminum compound.
As the silicon compounds, there may be exemplified #3 water glass, sodium orthosilicate, sodium metasilicate or the like.
The amount of the silicon compound added is 0.01 to 20% by weight (calculated as SiO2) based on the weight of the magnetic acicular particles. When the amount of the silicon compound added is less than 0.01% by weight, it may be difficult to sufficiently coat the surfaces of the magnetic acicular particles with hydroxides and/or oxides of silicon, thereby failing to improve the effective reduction of the carbon black desorption percentage. On the other hand, when the amount of the silicon compound added is more than 20% by weight, the coating effect is saturated and, therefore, it is meaningless to add such an excess amount of the silicon compound.
In the case where both the aluminum and silicon compounds are used in combination for the coating, the total amount of the aluminum and silicon compounds added is preferably 0.01 to 20% by weight (calculated as a sum of Al and SiO2) based on the weight of the magnetic acicular particles.
Next, the process for producing the magnetic recording medium according to the present invention is described.
The magnetic recording medium according to the first and second aspects of the present invention can be produced by an ordinary method, i.e., by coating the surface of the non-magnetic base film with a magnetic coating composition comprising black magnetic acicular composite particles, a binder resin, and a solvent to form a magnetic recording layer thereon, and then magnetically orienting the magnetic recording layer.
The magnetic recording medium according to the third to sixth aspects of the present invention can be produced by an ordinary method, i.e., by coating the surface of the non-magnetic base film with a non-magnetic coating composition comprising non-magnetic particles, a binder resin and a solvent to form a coating film thereon; drying the coating film to form a non-magnetic undercoat layer; coating the surface of the non-magnetic undercoat layer with a magnetic coating composition comprising black magnetic acicular composite particles, a binder resin and a solvent to form a magnetic recording layer thereon, and then magnetically orienting the magnetic recording layer.
Upon kneading and dispersing the non-magnetic coating composition and magnetic coating composition, as kneaders, there may be used, for example, twin-screw kneader, twin-screw extruder, pressure kneader, twin-roll mill, triple-roll mill or the like; and as dispersing devices, there may be used ball mill, sand grinder, attritor, disper, homogenizer, ultrasonic dispersing device or the like.
The coating of the non-magnetic coating composition and magnetic coating composition may be conducted using gravure coater, reverse-roll coater, slit coater, die coater or the like. The thus obtained coating film may be magnetically oriented using counter magnet, solenoid magnet or the like.
As the solvents, there may be used methyl ethyl ketone, toluene, cyclohexanone, methyl isobutyl ketone, tetrahydrofuran, a mixture of these solvents or the like.
The total amount of the solvent used is 65 to 1,000 parts by weight based on 100 parts by weight of the black magnetic acicular composite particles. When the amount of the solvent used is less than 65 parts by weight, the viscosity of the magnetic coating composition prepared therefrom becomes too high, thereby making it difficult to apply the magnetic coating composition. On the other hand, when the amount of the solvent used is more than 1,000 parts by weight, the amount of the solvent volatilized during the formation of the coating film becomes too large, thereby rendering the coating process industrially disadvantageous.
The one point of the present invention is the fact that when a single carbon black coat is firmly formed onto the surfaces of the core particles in an amount as large as from more than 10 to 40 parts by weight based on 100 parts by weight of the core particles, the obtained magnetic acicular composite particles can exhibit a well-controlled myristic acid-adsorption of 0.01 to 0.3 mg/m2.
The reason why the magnetic acicular composite particles of the present invention can exhibit a reduced myristic acid-adsorption, is considered as follows, though not clearly known yet. That is, due to the fact that the myristic acid-adsorption of the magnetic acicular particles cannot be reduced to not more than 0.3 mg/m2 in any of the cases where the carbon black desorption percentage is more than 20% even though the amount of carbon black adhered is more than 10 parts by weight, and where the amount of carbon black adhered is not more than 10 parts by weight even though the carbon black desorption percentage is not more than 20%, as described in Comparative Examples below, it is considered that many hydroxyl groups present on the surface of the core particles are prevented from being bonded with carboxyl groups of myristic acid which show a high affinity to the hydroxyl groups.
Also, the magnetic recording medium of the first and second aspect of the present invention using the above magnetic acicular particles according to the present invention can exhibit a low friction coefficient and an excellent running durability.
The reason why the magnetic recording medium of the first and second aspect of the present invention can show a reduced friction coefficient, is considered by the present inventors as follows. That is, since the amount of myristic acid adsorbed onto the surfaces of the magnetic acicular particles which are incorporated in a large amount into a magnetic recording layer thereof, is restricted to the specified range, an appropriate amount of myristic acid can be oozed onto the surface of the magnetic recording layer in a well-controlled condition for a long period of time, thereby effectively exhibiting a lubricating function thereof.
The reason why the magnetic recording medium of the first and second aspect of the present invention can show an excellent running durability, is considered by the present inventors as follows. That is, for the same reason as described above, an appropriate amount of myristic acid can be oozed onto the surface of the magnetic recording layer in a well-controlled condition, resulting in stable running durability of the magnetic recording medium.
Another point of the present invention is the fact that the magnetic recording medium of the third to sixth aspects which has a non-magnetic undercoat layer and is obtained by using the black magnetic acicular composite particles as magnetic particles, can exhibit a small light transmittance and a low surface electrical resistivity value even though the amount of carbon black incorporated in a magnetic recording layer thereof is reduced to as small a level as possible, and can be enhanced in surface smoothness of the magnetic recording layer.
The reason why the magnetic recording medium of the third to sixth aspects of the present invention can show a small light transmittance irrespective of a less amount of carbon black added thereto, is considered by the present inventors as follows. That is, carbon black fine particles usually tend to form agglomerates due to fineness thereof. However, in the black magnetic acicular composite particles of the present invention, since the carbon black fine particles can be uniformly and densely adhered in the form of the coating layer onto the surfaces of the core particles, carbon black can exhibit a function thereof more effectively.
The reason why the magnetic recording medium of the third to sixth aspects of the present invention can show a low surface electrical resistivity value irrespective of a less amount of carbon black added thereto, is considered by the present inventors as follows. That is, since the black magnetic acicular composite particles are uniformly dispersed in the coating film, the carbon black fine particles uniformly and densely adhered in the form of the coating layer onto the surfaces of the respective composite particles are continuously connected and contacted with each other in the coating film.
The reason why the magnetic recording medium of the third to sixth aspects of the present invention can show an excellent surface smoothness, is considered by the present inventors as follows. That is, in the black magnetic acicular composite particles of the present invention, the amount of carbon black fine particles desorbed or fallen-off from the surfaces of the particles is very small, and the amount of carbon black fine particles added into the magnetic recording layer of the magnetic recording medium can be reduced to as small a level as possible. For these reasons, the black magnetic acicular composite particles are prevented from being deteriorated in dispersibility in vehicle due to desorbed and liberated carbon black fine particles upon the production of magnetic coating composition. Further, the black magnetic acicular composite particles themselves are excellent in dispersibility in vehicle.
The magnetic recording medium of the third and fourth aspects according to the present invention in which the black magnetic acicular composite particles having a well-controlled myristic acid-adsorption are used, can exhibit a low friction coefficient and an excellent running durability.
The reason why the magnetic recording medium of the third and fourth aspects according to the present invention can be reduced in friction coefficient, is considered by the present inventors as follows. That is, by controlling the amount of myristic acid adsorbed onto the surfaces of the black magnetic acicular composite particles which are incorporated in a large amount into a magnetic recording layer of the magnetic recording medium, to the specified range, an appropriate amount of myristic acid can be oozed onto the surface of the magnetic recording layer in a well-controlled condition for a long period of time, thereby effectively exhibiting a good lubricating function thereof.
The reason why the magnetic recording medium of the third and fourth aspects of the present invention has an excellent running durability, is considered by the present inventors as follows. That is, for the same reason as described above, an appropriate amount of myristic acid can be oozed onto the surface of the magnetic recording layer in a well-controlled condition, resulting in stable running durability of the magnetic recording medium.
Further, the black magnetic acicular composite particles of the present invention can exhibit an excellent dispersibility in vehicle, a more excellent blackness, a lower volume resistivity value and a well-controlled myristic acid-adsorption. Therefore, when the particles are used for the production of magnetic recording medium, the obtained magnetic recording medium can exhibits a smooth surface, a more excellent blackness and a lower surface electrical resistivity value, and can be well-controlled in amount of myristic acid oozed onto the surface of a magnetic recording layer. Accordingly, the magnetic acicular composite particles of the present invention is suitable as magnetic acicular particles for magnetic recording media.
By using the above black magnetic acicular composite particles, the magnetic recording medium according to the present invention can exhibit not only a smooth surface, a smaller light transmittance and a lower surface electrical resistivity value, but also a small friction coefficient and an excellent running durability. Therefore, the magnetic recording medium of the present invention is suitable as those for high-density recording.
Also, in the magnetic recording medium of the third and fourth aspects of the present invention, the non-magnetic undercoat layer is formed, and the black magnetic acicular composite particles having an excellent blackness and a low volume resistivity value are used as magnetic particles therefor. Therefore, the obtained magnetic recording medium can exhibit a small light transmittance and a low surface electrical resistivity value. Further, since the amount of carbon black fine particles incorporated into the magnetic recording layer is reduced to as small a level as possible and the black magnetic acicular composite particles themselves are enhanced in dispersibility in vehicle, the obtained magnetic recording medium can exhibit a smooth surface. Accordingly, the magnetic recording medium of the present invention is suitable as those for high-density recording.
Further, the black magnetic acicular composite particles adhered with a large amount of carbon black, exhibit a well-controlled myristic acid-adsorption. Therefore, the magnetic recording medium of the present invention using the above black magnetic acicular composite particles as magnetic particles, can exhibit a small friction coefficient and an excellent running durability in addition to the above-described properties. Accordingly, the magnetic recording medium of the present invention is suitable as those for high-density recording.